h0lx - 17-2-2007 at 12:48
I just looked through my supplier's list and found cyclohexanone for a cheap price. I was wondering if it would form peroxides like acetone or MEK. If
possible, would it be acid catalysed too? Has anybody tired it? Should I give it a shot?
Bromine - 17-2-2007 at 14:44
be extremly carful, for some peroxides even slightest friction or shock or even a sun light is enough for set them of.
Ozone - 17-2-2007 at 17:46
To my knowledge, NO.
It sits there like a rock.
Cheers,
O3
chemrox - 17-2-2007 at 19:22
Where did this concern come from? I would welcome a cheap source of it too. U2U?
Anyway, I've used gallons of the stuff in the past and never had any problems with it. Sloppy storage in metal cans and all...
h0lx - 17-2-2007 at 23:38
But is the peroxide energetic? Would it even detonate?
Ozone - 18-2-2007 at 08:51
"Cyclohexanone peroxide" is probably a mixture of the hydroperoxide, peroxyacid and the dimer (or higher) corresponding to 1,1'-peroxydiclohexanol. It
is used as a free radical initiator for various resins and is also frequently compounded with MEKP (~20% MEKP + ~10% CHP) and sold for a similar
purpose. CHP appearsto be rather stable (like H2O2) unless organic material or metals are introduced. Still, I prefer to be cautious with the organic
peroxides (even benzoyl peroxide, which I use frequently) because they can (and do) occasionally trigger unexpected explosions.
The next several posts will contain the original papers of Brown, et al (1954) for your enjoyment. It seems that high temperatures (95-105°C) and a
catalyst are required to get the peroxides. Your cyclohexanone stored at rt in an amber bottle will not be likely to contain peroxides in any
significant quantity.
Cheers,
O3
[Edited on 18-2-2007 by Ozone]
Attachment: cycloalkanone peroxides_I.pdf (544kB)
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Ozone - 18-2-2007 at 08:54
And... Part II.
O3
Attachment: cycloalkanone peroxides_II.pdf (216kB)
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Axt - 18-4-2007 at 03:24
If cyclohexanone bears any analogy to that of cyclopentanone and I expect that it does, treating it with H2O2/mineral acid as you would for acetone
peroxide does result in a peroxide precipitate. This is described in a patent which i cant find at this time. Though the order of addition was
important, adding peroxide/cyclopentanone to HNO3 gave a different product then adding cyclopentanone to peroxide/HNO3, one resulted in a resin the
other crystals. The correct order i cannot remember but I'll dig up the patent.
Cyclopentanone peroxide should be more energetic then a cyclohexanone analog, theres a recent topic on decarboxylation of adipic acid with barium salt
catalyst to form cyclopentanone. http://www.sciencemadness.org/talk/viewthread.php?tid=5564&a... a more available catalyst may be sodium borate, boric acid or Al2O3 (see
US5856581).
[Edited on 1-5-2007 by Axt]
Axt - 30-4-2007 at 05:59
I was mistaken, the patent was specific to cyclohexanone not cyclopentanone. The cyclohexanone was added to a mixture of peroxide and nitric acid to
form a crystalline precipitate. Patent is attached.
US2298405 mentions a dimeric cyclopentanone peroxide, it is said to "explode violently". Though the method they use isn't terribly practical, they use
no acid catalyst, isolate the hydroperoxide and let it sit. I'd just try the method mentioned for the cyclohexanone in US2750421.
Attachment: cyclohexyl peroxides - US2750421.pdf (111kB)
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Ozone - 30-4-2007 at 19:29
Shoot! I thought h0lx was concerned about his bottle of cyclohexanone developing peroxides (which it won't, to any significant effect). It *will*
peroxidize with H2O2, etc.
Not that I recommend this
. It's a nice radical initiator, after all.
Be careful,
O3